EP0165100B1 - Tri(cyclopentadienyl)cerium and process for its preparation - Google Patents

Tri(cyclopentadienyl)cerium and process for its preparation Download PDF

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EP0165100B1
EP0165100B1 EP85400829A EP85400829A EP0165100B1 EP 0165100 B1 EP0165100 B1 EP 0165100B1 EP 85400829 A EP85400829 A EP 85400829A EP 85400829 A EP85400829 A EP 85400829A EP 0165100 B1 EP0165100 B1 EP 0165100B1
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cyclopentadienyl
cerium
process according
alkali metal
complex
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EP0165100A1 (en
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Peter Gradeff
Fred Schreiber
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System

Definitions

  • the present invention relates to tri (cyclopentadienyl) cerium and its preparation process.
  • the tri (cyclopentadienyl) cerium III is a crystalline solid; it is thermally stable up to a temperature of at least 435 ° C, the temperature at which it melts; it decomposes with water to give cyclopentadiene and cerux hydroxide; it is soluble in tetrahydrofuran and in dimethoxyethane.
  • the tri (cyclopentadienyl) cerium reacts quickly with air, it instantly darkens even when there is only traces of oxygen. For more details, see the article by BIRMINGHAM and WILKINSON published in the Journal of the American Chemical Society 78.42 (1956).
  • KALSOTRA et al. describe the sulfur tri (cyclopentadienyl) cerium (IV) derivatives [Journal of Inorganic Nuclear Chemistry 35, 3966 - 3968 (1973)], the pseudohalogenated tri (cyclopentadienyl) cerium (IV) complexes [Journal of Inorganic Nuclear Chemistry 34, 2265 - 2269 (1972)], alkoxy derivatives of cerium (IV) [Journal of Organometallic Chemistry 63, 301 - 303 (1973)], phenolic derivatives of tri (cyclopentadienyl) cerium (IV) [Journal of the Chinese Chemical Society 19 , 197 - 202 (1972)], the carboxylato complexes of tri (cyclopentadienyl) cerium (IV) chloride [Journal of the Chinese Chemical Society 18, 189 - 197 (1971)], the alkoxy derivatives of tri (cyclopentadienyl) cerium
  • DEACON et al. reproduced the synthesis of KALSOTRA et al. and found that the reaction product was not tetra (cyclopentadienyl) cerium but tri (cyclopentadienyl) cerium.
  • KALSOTRA et al. and DEACON et al. used to prepare dipyridinium hexachlorocerate (IV), the method described by BRADLEY et al. in J. Chem. Soc. 1956, 2260. This method is tedious but it appears, according to the authors, to be the only one which can lead to a product of satisfactory quality.
  • the cerium dioxide is transformed into ceric ammonium sulphate.
  • a pure ceric hydroxide is precipitated from an aqueous solution of ceric ammonium sulphate and the precipitate is washed.
  • the complex is filtered and dried.
  • the complex is used to prepare the alkoxides according to BRADLEY et al., And the (cyclopentadienyl) cerium derivatives according to KALSTORA et al. and DEACON et al.
  • the process according to the invention for the preparation of tri (cyclopentadienyl) cerium as well as mono- and di (cyclopentadienyl) cerium intermediates is characterized by the fact that it consists in reacting an alkali metal cyclopentadienyl complex with a ceric ammonium nitrate dissolved in an inert organic solvent so that the tri (cyclopentadienyl) cerium or that is formed according to the order of addition of the reagents, successively and in stages, mono (cyclopentadienyl) cerium dinitrate, di (cyclopentadienyl) cerium mononitrate and tri (cyclopentadienyl) cerium .
  • cyclopentadienyl alkali metal complex When a cyclopentadienyl alkali metal complex is added to a solution of ceric ammonium nitrate, mono (cyclopentadienyl) cerium dinitrate, CeCp (N0 3 ) 2 , di (mononitrate) is formed successively and in stages. cyclopentadienyl) cerium, CeCp 2 NO 3 and of the tri (cyclopentadienyl) cerium, CeC p 3 .
  • alkali metal cyclopentadienyl complex used depends on the desired cerium III cyclopentadienyl complex.
  • reaction (b) does not seem to be very rapid: the evolution of ammonia can be observed long after all the reactions have ended. It appears that reaction (a) is the fastest. Indeed, it is obvious that this reaction must be completed before any other takes place.
  • the process is preferably carried out by adding a solution of ceric ammonium nitrate in an inert organic solvent to a slurry of alkali metal cyclopentadienyl complex in the same solvent.
  • any alkali metal cyclopentadienyl complex can be used such as (cyclopentadienyl) sodium, (cyclopentadienyl) potassium, (cyclopentadienyl) cesium, (cyclopentadienyl) lithium.
  • (cyclopentadienyl) sodium is chosen.
  • the use of an excess of NaCp relative to the theoretical amount results in the formation of dark purple complexes which are of no interest.
  • the desired product Ce (Cp) 3 can be recovered by adding to the complex, the necessary quantity of ceric ammonium nitrate.
  • the desired end product is Ce (Cp) 3 it is easier to add the ceric ammonium nitrate solution to the NaCp slurry than the reverse. As long as the NaCp complex is in excess, for most of the reaction time.
  • the reaction can be carried out in any suitable inert organic solvent of ceric ammonium nitrate.
  • the alkali metal cyclopentadienyl complex can be in solution or suspension in the same solvent. Tetrahydrofuran and dimethoxyethane are easily accessible and are preferably chosen. Other solvents such as benzene, hexane, acetonitrile and other glycol ethers can be used.
  • an inert organic solvent is used in an amount sufficient to dissolve the ceric ammonium nitrate and the (cyclopentadienyl) cerium formed.
  • the reaction is carried out at room temperature. Lower temperatures ranging from about -10 to about + 25 ° C can be used, but then the reaction will generally be slow. The reaction also takes place at elevated temperatures of up to about 250 ° C, but it is easier to work at the reflux temperature of the solvent. The reaction is rapid and is generally completed in less than an hour and can take up to approximately 10 hours.
  • the reaction medium contains the nitrate corresponding to the alkali metal such as, for example, sodium nitrate.
  • the salt is insoluble in the reaction medium and precipitates.
  • the nitrate can be separated by filtration, recover the filtrate, evaporate the solvent, wash and dry the solid residue to recover the mono-, di- or tri (cyclopentadienyl) cerium according to the stage of the reaction.
  • mono-, di- or tri (cyclopentadienyl) cerium can be used in the form in which they exist in the reaction medium, at the end of the reaction, that is to say without isolating them. of the reaction medium or separate them from the by-products which avoids processing and handling costs.
  • the (cyclopentadienyl) sodium is prepared by adding, in fractions of 5 cm 3 , a solution of cyclopentadiene (12.56 g at about 95%, 0.1805 motel in dimethoxyethane (27.1 g) at -78 ° C, to a slurry of sodium hydride (7.45 g, 0.1820 mole, dispersion in oil at 58.62%) in dimethoxyethane (98.2 g) under argon, at -2 ° C. The temperature of the reaction medium is kept between -10 and -20 ° C. by a cooling bath. The evolution of hydrogen is very important. When the addition is complete, the pink-gray (cyclopentadienyl) sodium slurry is allowed to warm up to at room temperature.
  • the filtrate is a golden-brown solution of tri (cyclopentadienyl) cerium in dimethoxyethane.
  • the tri (cyclopentadienyl) cerium is recovered after evaporating the solvent.
  • the filtrate contains the Ce (NO 3 ) 2 Cp complex.
  • the dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.
  • the filtrate contains the Ce (N0 3 ) 2 Cp complex.
  • the dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.
  • the filtrate contains the CeNO 3 (Cp) 2 complex.
  • the dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.
  • the filtrate contains the Ce (N0 3 ) 2 C P complex.
  • the dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.

Description

La présente invention concerne le tri(cyclopentadiényl)cérium et son procédé de préparation.The present invention relates to tri (cyclopentadienyl) cerium and its preparation process.

WILKINSON et BIRMINGHAM [Journal of the American Chemical Society 76, 6210 (1954)] ont montré que le cyclopentadiène forme des composés organométalliques avec un certain nombre de métaux auxquels le noyau cyclopentadiène peut être lié de trois façons:

  • (a) à de nombreux métaux de transition, par la liaison covalente à deux électrons, dénommée "liaison sandwich";
  • (b) par une liaison covalente entre le métal et un seul atome de carbone du noyau. Les composés de (cyclopentadiényl)silicium peuvent être de ce type;
  • (c) par des liaisons ioniques.
WILKINSON and BIRMINGHAM [Journal of the American Chemical Society 76, 6210 (1954)] have shown that cyclopentadiene forms organometallic compounds with a number of metals to which the cyclopentadiene nucleus can be linked in three ways:
  • (a) to many transition metals, by the covalent bond with two electrons, called "sandwich bond";
  • (b) by a covalent bond between the metal and a single carbon atom in the nucleus. The (cyclopentadienyl) silicon compounds can be of this type;
  • (c) by ionic bonds.

En mélangeant sous agitation, le chlorure anhydre du métal avec le (cyclopentadiényl)sodium dans une solution de tétrahydrofuranne, en éliminant le solvant et en chauffant ensuite le résidu à une température comprise entre 200 et 250°C sous vide, il se forme des complexes tricyclopentadiényliques de formule (C5H5)3M dans laquelle M comprend le cérium (III). Le tri(cyclopentadiényl)cérium III est un solide cristallin; il est thermiquement stable jusqu'à une température d'au moins 435°C, température à laquelle il fond; il se décompose avec l'eau pour donner du cyclopentadiène et de l'hydroxyde cérux; il est soluble dans le tétrahydrofuranne et dans le diméthoxyéthane. Le tri(cyclopentadiényl)cérium réagit rapidement avec l'air, il noircit instantanément même lorsqu'il n'est en présence que de traces d'oxygène. Pour plus de détails on se référera à l'article de BIRMINGHAM et WILKINSON publié dans le Journal of the American Chemical Society 78,42 (1956).By mixing, with stirring, the anhydrous chloride of the metal with (cyclopentadienyl) sodium in a solution of tetrahydrofuran, removing the solvent and then heating the residue to a temperature between 200 and 250 ° C. under vacuum, complexes are formed. tricyclopentadienyls of formula (C 5 H 5 ) 3 M in which M comprises cerium (III). The tri (cyclopentadienyl) cerium III is a crystalline solid; it is thermally stable up to a temperature of at least 435 ° C, the temperature at which it melts; it decomposes with water to give cyclopentadiene and cerux hydroxide; it is soluble in tetrahydrofuran and in dimethoxyethane. The tri (cyclopentadienyl) cerium reacts quickly with air, it instantly darkens even when there is only traces of oxygen. For more details, see the article by BIRMINGHAM and WILKINSON published in the Journal of the American Chemical Society 78.42 (1956).

KALSOTRA, ANAND, MULTANI et JAIN ont décrit dans le Journal of Organometallic Chemistry 28, 87 - 89 (1971) la préparation du tétra(cyclopentadiényl)cérium par réaction du (cyclopentadiényl)sodium dans le tétrahydrofuranne avec l'hexachlorure de dipyridinium cérium. La réaction est conduite dans des conditions anhydres. Le (cyclopentadiényl)sodium est ajouté à une solution d'hexachlorure de dipyridinium cérium dans le tétrahydrofuranne, et on manitient le mélange sous reflux entre 100 et 110°C et sous forte agitation pendant 10 à 12 heures jusqu'à ce qu'il se forme un produit brun-rougeâtre. On filtre le mélange refroidi sur verre fritté et on lave le résidu avec du tétrahydrofuranne. Après évaporation du solvant, on obtient une pâte brune épaisse qui est cristallisée dans de l'éther de pétrole léger. On obtient un composé cristallin rouge-orange, dont la couleur rappelle d'une manière frappante celle du tri(cyclopentadiényl)cérium décrit par BIRMINGHAM et WILKINSON en 1956. On se reportera pour plus d'informations relatives à la préparation dudit produit à Israel Journal of Chemistry 9, 569 - 572 (1971).KALSOTRA, ANAND, MULTANI and JAIN described in the Journal of Organometallic Chemistry 28, 87 - 89 (1971) the preparation of tetra (cyclopentadienyl) cerium by reaction of (cyclopentadienyl) sodium in tetrahydrofuran with dipyridinium cerium hexachloride. The reaction is carried out under anhydrous conditions. The (cyclopentadienyl) sodium is added to a solution of dipyridinium cerium hexachloride in tetrahydrofuran, and the mixture is handled under reflux between 100 and 110 ° C and with vigorous stirring for 10 to 12 hours until it forms a reddish-brown product. The cooled mixture is filtered on sintered glass and the residue is washed with tetrahydrofuran. After evaporation of the solvent, a thick brown paste is obtained which is crystallized from light petroleum ether. A red-orange crystalline compound is obtained, the color of which strikingly recalls that of the tri (cyclopentadienyl) cerium described by BIRMINGHAM and WILKINSON in 1956. For more information relating to the preparation of the said product, see Israel Journal. of Chemistry 9, 569-572 (1971).

Dans une série de publications, KALSOTRA et coll. décrivent les dérivés soufrés de tri(cyclopentadiényl)cérium (IV) [Journal of Inorganic Nuclear Chemistry 35, 3966 - 3968 (1973)], les complexes pseudohalogénés de tri(cyclopentadiényl)cérium (IV) [Journal of Inorganic Nuclear Chemistry 34, 2265 - 2269 (1972)], les dérivés alkoxy du cérium (IV) [Journal of Organometallic Chemistry 63, 301 - 303 (1973)], les dérivés phénoliques du tri(cyclopentadiényl)cérium (IV) [Journal of the Chinese Chemical Society 19, 197 - 202 (1972)], les complexes carboxylato de chlorure de tri(cyclopentadiényl)cérium (IV) [Journal of the Chinese Chemical Society 18, 189 - 197 (1971)], les dérivés alkoxy du tri(cyclopentadiényl)cérium (IV) [Journal of the Chinese Chemical Society 20, 171 - 173 (1973)].In a series of publications, KALSOTRA et al. describe the sulfur tri (cyclopentadienyl) cerium (IV) derivatives [Journal of Inorganic Nuclear Chemistry 35, 3966 - 3968 (1973)], the pseudohalogenated tri (cyclopentadienyl) cerium (IV) complexes [Journal of Inorganic Nuclear Chemistry 34, 2265 - 2269 (1972)], alkoxy derivatives of cerium (IV) [Journal of Organometallic Chemistry 63, 301 - 303 (1973)], phenolic derivatives of tri (cyclopentadienyl) cerium (IV) [Journal of the Chinese Chemical Society 19 , 197 - 202 (1972)], the carboxylato complexes of tri (cyclopentadienyl) cerium (IV) chloride [Journal of the Chinese Chemical Society 18, 189 - 197 (1971)], the alkoxy derivatives of tri (cyclopentadienyl) cerium ( IV) [Journal of the Chinese Chemical Society 20, 171 - 173 (1973)].

Cependant, DEACON, TUONG et VINCE dans POLYHEDRON 2,969 - 970 (1983) ont réfuté ces auteurs pour ce qui a trait à la synthèse du tétrakis(cyclopentadiényl)cérium (IV). En effet, ils ont montré que la réaction du (cyclopentadiényl)sodium avec l'hexachlorocérate (IV) de dipyridinium dans le tétrahydrofuranne conduit non pas au tétrakis(cyclopentadiényl)cérium (IV) mais au tris(cyclopentadiényl)cérium (III). DEACON et coll., ont mis en évidence que les propriétés d'un dérivé tri(cyclopentadiényl)cérium propoxy obtenu à partir de cette source, diffère on couleur, volatilité, absorption IR du même composé préparé par alcoolyse de tétra(cyclopentadiényl)cérium ou de chlorure de tri(cyclopentadiényl)cérium; ils font remarquer en outre qu'il est difficile de concilier le clivage du tétra(cyclopentadiényl)cérium par l'isopropanol et la stabilité à l'eau et aux acides dilués.However, DEACON, TUONG and VINCE in POLYHEDRON 2,969 - 970 (1983) refuted these authors with regard to the synthesis of tetrakis (cyclopentadienyl) cerium (IV). In fact, they have shown that the reaction of (cyclopentadienyl) sodium with dipyridinium hexachlorocerate (IV) in tetrahydrofuran leads not to tetrakis (cyclopentadienyl) cerium (IV) but to tris (cyclopentadienyl) cerium (III). DEACON et al., Have demonstrated that the properties of a tri (cyclopentadienyl) cerium propoxy derivative obtained from this source, differ in color, volatility, IR absorption of the same compound prepared by tetra (cyclopentadienyl) cerium alcoholysis or tri (cyclopentadienyl) cerium chloride; they also point out that it is difficult to reconcile the cleavage of tetra (cyclopentadienyl) cerium by isopropanol and the stability to water and to dilute acids.

DEACON et coll. ont reproduit la synthèse de KALSOTRA et coll. et ont trouvé que le produit réactionnel était non pas le tétra(cyclopentadiényl)cérium mais le tri(cyclopentadiényl)cérium.DEACON et al. reproduced the synthesis of KALSOTRA et al. and found that the reaction product was not tetra (cyclopentadienyl) cerium but tri (cyclopentadienyl) cerium.

KALSOTRA et coll. et DEACON et coll. ont utilisé pour préparer l'hexachlorocérate (IV) de dipyridinium, la méthode décrite par BRADLEY et coll. dans J. Chem. Soc. 1956, 2260. Cette méthode est fastidieuse mais elle apparaît, selon les auteurs, être la seule qui puisse conduire à un produit de qualité satisfaisante. Dans un premier temps, on transforme le dioxyde de cérium en sulfate cérique d'ammonium. On précipite un hydroxyde cérique pur à partir d'une solution aqueuse de sulfate cérique d'ammonium et on lave le précipité. On traite le précipité fraîchement préparé et mis en suspension dans de l'alcool absolu, avec de l'acide chlorhydrique anhydre et on ajoute de la pyridine qui forme un complexe insoluble d'hexachlorure de dipyridinium cérium (PyH)2CeCI6. On filtre le complexe et on le sèche. On utilise le complexe pour préparer les alkoxydes selon BRADLEY et coll., et les dérivés de (cyclopentadiényl)cérium selon KALSTORA et coll. et DEACON et coll.KALSOTRA et al. and DEACON et al. used to prepare dipyridinium hexachlorocerate (IV), the method described by BRADLEY et al. in J. Chem. Soc. 1956, 2260. This method is tedious but it appears, according to the authors, to be the only one which can lead to a product of satisfactory quality. Firstly, the cerium dioxide is transformed into ceric ammonium sulphate. A pure ceric hydroxide is precipitated from an aqueous solution of ceric ammonium sulphate and the precipitate is washed. The freshly prepared precipitate, suspended in absolute alcohol, is treated with anhydrous hydrochloric acid and pyridine is added, which forms an insoluble complex of dipyridinium cerium hexachloride (PyH) 2 CeCI 6 . The complex is filtered and dried. The complex is used to prepare the alkoxides according to BRADLEY et al., And the (cyclopentadienyl) cerium derivatives according to KALSTORA et al. and DEACON et al.

Conformément à la présente invention, on met en oeuvre pour obtenir des complexes cyclopentadiényliques de cérium (III), avec un bon rendement, non pas l'hexachlorocérate de dipyridinium mais le nitrate cérique d'ammonium, produit disponible dans le commerce et relativement bon marché. Au cours du procédé, le cérium (IV) est réduit en cérium (III).In accordance with the present invention, use is made to obtain cyclopentadienyl complexes of cerium (III), with a good yield, not dipyridinium hexachlorocerate but ceric ammonium nitrate, a product available commercially and relatively inexpensive. . During the process, the cerium (IV) is reduced to cerium (III).

Le procédé, selon l'invention, de préparation du tri(cyclopentadiényl)cérium aussi bien que des intermédiaires mono- et di(cyclopentadiényl)cérium est caractérisé par le fait qu'il consiste à faire réagir un complexe cyclopentadiénylique de métal alcalin avec un nitrate cérique d'ammonium en solution dans un solvant organique inerte de telle sorte que l'on obtienne le tri(cyclopentadiényl)cérium ou que l'on forme selon l'ordre d'addition des réactifs, successivement et par étape, le dinitrate de mono(cyclopentadiényl)cérium, le mononitrate de di(cyclopentadiényl)cérium et le tri(cyclopentadiényl)cérium.The process according to the invention for the preparation of tri (cyclopentadienyl) cerium as well as mono- and di (cyclopentadienyl) cerium intermediates is characterized by the fact that it consists in reacting an alkali metal cyclopentadienyl complex with a ceric ammonium nitrate dissolved in an inert organic solvent so that the tri (cyclopentadienyl) cerium or that is formed according to the order of addition of the reagents, successively and in stages, mono (cyclopentadienyl) cerium dinitrate, di (cyclopentadienyl) cerium mononitrate and tri (cyclopentadienyl) cerium .

Lorsque l'on ajoute un complexe cyclopentadiénylique de métal alcalin dans une solution de nitrate cérique d'ammonium, se forme, successivement et par étape, du dinitrate de mono(cyclopentadiényl)cérium, CeCp(N03)2, du mononitrate de di(cyclopentadiényl)cérium, CeCp2N03 et du tri(cyclopentadiényl)cérium, CeCp 3.When a cyclopentadienyl alkali metal complex is added to a solution of ceric ammonium nitrate, mono (cyclopentadienyl) cerium dinitrate, CeCp (N0 3 ) 2 , di (mononitrate) is formed successively and in stages. cyclopentadienyl) cerium, CeCp 2 NO 3 and of the tri (cyclopentadienyl) cerium, CeC p 3 .

La quantité de complexe cyclopentadiénylique de métal alcalin mise en oeuvre est fonction du complexe cyclopentadiénylique de cérium III désiré.The quantity of alkali metal cyclopentadienyl complex used depends on the desired cerium III cyclopentadienyl complex.

Selon le cas, elle doit être suffisante pour obtenir du dinitrate de mono(cyclopentadiényl)cérium, du mononitrate de di(cyclopentadiényl)céium ou du tricoclopentaiénylcérium.Depending on the case, it must be sufficient to obtain mono (cyclopentadienyl) cerium dinitrate, di (cyclopentadienyl) cerium mononitrate or tricoclopentaienyl cerium.

Lorsque l'on ajoute un complexe cyclopentadiénylique de métal alcalin tel que le(cyclopentadiényl)sodium, NaCp, à une solution de nitrate cérique d'ammonium, il peut se produire plusieurs réactions plus ou moins concurrentes:

  • (a) 2Ce(N03)4 + 2NaCp → (2Ce(NO3)3Cp] [2Ce(NO3)3Cp] → 2Ce(N03)3 + CP2
  • (b) NH4N03 + NaCp - NaN03 + NH3 + CpH
  • (c) 2Ce(N03)4 + 2CpH + 2NH3 - 2Ce(NO3)3 + CP2 + 2NH4N03
  • (d) Ce(NO3)3 + NaCp - Ce(N03)2Cp + NaN03
  • (e) Ce(N03)2Cp + NaCp - Ce(N03)Cp2 + NaN03
  • (f) Ce(N03)Cp2 + NaCp → Ce(Cp)3 + NaN03
When adding an alkali metal cyclopentadienyl complex such as (cyclopentadienyl) sodium, NaCp, to a solution of ceric ammonium nitrate, several more or less competing reactions can occur:
  • ( a) 2Ce (N03) 4 + 2NaC p → (2Ce (NO 3 ) 3 Cp] [2Ce (NO 3 ) 3 Cp] → 2Ce (N0 3 ) 3 + CP 2
  • (b) NH 4 N0 3 + NaCp - NaN0 3 + NH 3 + CpH
  • (c) 2Ce (N0 3 ) 4 + 2CpH + 2NH 3 - 2Ce (NO 3 ) 3 + C P2 + 2NH 4 N0 3
  • (d) Ce (NO 3 ) 3 + NaCp - Ce (N0 3 ) 2 Cp + NaN0 3
  • (e) Ce (N0 3 ) 2 Cp + NaCp - Ce (N0 3 ) Cp 2 + NaN0 3
  • (f) Ce (N0 3 ) Cp 2 + NaCp → Ce (Cp) 3 + NaN0 3

L'équation réactionnelle globale est la suivante:

  • 2[Ce(N03)42NH4N03] + 12NaCp → 2Ce(Cp)3 + 4CpH + (Cp)2 + 12NaN03 + 4NH3
The overall reaction equation is as follows:
  • 2 [Ce (N0 3 ) 4 2NH 4 N0 3] + 12NaCp → 2Ce (Cp) 3 + 4CpH + (Cp) 2 + 12NaN0 3 + 4NH 3

Ces réactions permettent de se faire une idée du mécanisme éventuel qui peut suivre ou non ce modèle.These reactions give an idea of the possible mechanism which may or may not follow this model.

Par exemple, la réaction (b) ne semble pas très rapide: on peut observer le dégagement d'ammoniac longtemps après la fin de toutes les réactions. Il apparaît que la réaction (a) est la plus rapide. En effet, il est évident que cette réaction doit être terminée avant que toute autre n'ait lieu.For example, reaction (b) does not seem to be very rapid: the evolution of ammonia can be observed long after all the reactions have ended. It appears that reaction (a) is the fastest. Indeed, it is obvious that this reaction must be completed before any other takes place.

Lorsque l'on inverse l'ordre d'addition et que l'on ajoute la solution de nitrate cérique d'ammonium dans un solvant organique inerte à une bouillie de complexe cyclopentadiénylique de métal alcalin dans un solvant organique inerte, bien que les réactions soient complexes, on obtient directement le produit final Ce(Cp)3, sans passer par des étapes intermédiaires.When the order of addition is reversed and the solution of ceric ammonium nitrate in an inert organic solvent is added to a slurry of alkali metal cyclopentadienyl complex in an inert organic solvent, although the reactions are complex, the final product Ce (Cp) 3 is obtained directly, without going through intermediate steps.

On conduit, de préférence, le procédé en ajoutant une solution de nitrate cérique d'ammonium dans un solvant organique inerte à une bouillie de complexe cyclopentadiénylique de métal alcalin dans le même solvant.The process is preferably carried out by adding a solution of ceric ammonium nitrate in an inert organic solvent to a slurry of alkali metal cyclopentadienyl complex in the same solvent.

On peut utiliser n'importe quel complexe cyclopentadiénylique de métal alcalin tels que le (cyclopentadiényl)sodium, le (cyclopentadiényl)potassium, le (cyclopentadiényl)césium, le (cyclo- pentadiényl)lithium. On choisit préférentiellement le (cyclopentadiényl)sodium. La mise en oeuvre d'un excès de NaCp par rapport à la quantité théorique entraîne la formation de complexes pourpre-foncé qui sont sans intérêt. On peut récupérer le produit recherché Ce(Cp)3 en ajoutant au complexe, la quantité nécessaire de nitrate cérique d'ammonium.Any alkali metal cyclopentadienyl complex can be used such as (cyclopentadienyl) sodium, (cyclopentadienyl) potassium, (cyclopentadienyl) cesium, (cyclopentadienyl) lithium. Preferably, (cyclopentadienyl) sodium is chosen. The use of an excess of NaCp relative to the theoretical amount results in the formation of dark purple complexes which are of no interest. The desired product Ce (Cp) 3 can be recovered by adding to the complex, the necessary quantity of ceric ammonium nitrate.

Lorsque le produit final souhaité est Ce(Cp)3 il est plus facile d'ajouter la solution de nitrate cérique d'ammonium à la bouillie de NaCp que l'inverse. Tant que le complexe NaCp est en exces, pendant la plus grande partie de la durée réactionnelle.When the desired end product is Ce (Cp) 3 it is easier to add the ceric ammonium nitrate solution to the NaCp slurry than the reverse. As long as the NaCp complex is in excess, for most of the reaction time.

On peut conduire la réaction dans tout solvant organique inerte approprié du nitrate cérique d'ammonium. Le complexe cyclopentadiénylique de métal alcalin peut être en solution ou suspension dans le même solvant. Le tétrahydrofuranne et le diméthoxyéthane sont aisément accessibles et sont choisis de préférence. On peut utiliser d'autres solvants tels que le benzène, l'hexane, l'acétonitrile et d'autres éthers glycoliques.The reaction can be carried out in any suitable inert organic solvent of ceric ammonium nitrate. The alkali metal cyclopentadienyl complex can be in solution or suspension in the same solvent. Tetrahydrofuran and dimethoxyethane are easily accessible and are preferably chosen. Other solvents such as benzene, hexane, acetonitrile and other glycol ethers can be used.

On utilise, de préférence, un solvant organique inerte en quantité suffisante pour dissoudre le nitrate cérique d'ammonium et le (cyclopentadiényl)cérium formé.Preferably, an inert organic solvent is used in an amount sufficient to dissolve the ceric ammonium nitrate and the (cyclopentadienyl) cerium formed.

On effectue la réaction à température ambiante. On peut mettre en oeuvre des températures plus basses allant d'environ - 10 à environ + 25°C, mais alors la réaction sera généralement lente. La réaction a lieu également à des températures élevées pouvant atteindre jusqu'à environ 250°C, mais il est plus aisé de travailler à la température de reflux du solvant. La réaction est rapide et est généralement terminée en moins d'une heure et peut durer jusqu'à 10 heures environ.The reaction is carried out at room temperature. Lower temperatures ranging from about -10 to about + 25 ° C can be used, but then the reaction will generally be slow. The reaction also takes place at elevated temperatures of up to about 250 ° C, but it is easier to work at the reflux temperature of the solvent. The reaction is rapid and is generally completed in less than an hour and can take up to approximately 10 hours.

Le milieu réactionnel contient le nitrate correspondant au métal alcalin tel que, par exemple, le nitrate de sodium. Le sel est insoluble dans le milieu réactionnel et précipite. On peut séparer le nitrate par filtration, récupérer le filtrat, évaporer le solvant, laver et sécher le résidu solide pour récoupérer le mono-, di- ou tri(cyclopentadiényl)cérium selon le stade de la réaction.The reaction medium contains the nitrate corresponding to the alkali metal such as, for example, sodium nitrate. The salt is insoluble in the reaction medium and precipitates. The nitrate can be separated by filtration, recover the filtrate, evaporate the solvent, wash and dry the solid residue to recover the mono-, di- or tri (cyclopentadienyl) cerium according to the stage of the reaction.

Pour certaines applications, on peut utiliser le mono-, le di- ou le tri(cyclopentadiényl)cérium sous la forme sous laquelle ils existent dans le milieu réactionnel, à la fin de la réaction, c'est-à-dire sans les isoler du milieu réactionnel ou les séparer des sous-produits ce qui évite des coûts de traitement et de manipulation.For certain applications, mono-, di- or tri (cyclopentadienyl) cerium can be used in the form in which they exist in the reaction medium, at the end of the reaction, that is to say without isolating them. of the reaction medium or separate them from the by-products which avoids processing and handling costs.

Les exemples qui suivent, illustrent un mode de réalisation préférentielle de l'invention mais en aucun cas, ils ne limitent la portée de l'invention.The examples which follow illustrate a preferred embodiment of the invention but in no way limit the scope of the invention.

Exemple 1Example 1

On prépare le (cyclopentadiényl)sodium en ajoutant, par fractions de 5 cm3, une solution de cyclopentadiène (12,56 g à environ 95%, 0,1805 motel dans du diméthoxyéthane (27,1 g) à -78°C, à une bouillie d'hydrure de sodium (7,45 g, 0,1820 mole, dispersion dans l'huile à 58,62 %) dans du diméthoxyéthane (98,2 g) sous argon, à -2°C. La température du milieu réactionnel est maintenue entre -10 et -20°C par un bain réfrigérant. Le dégagement d'hydrogène est très important. Lorsque l'addition est terminée, on laisse la bouillie rose-gris de (cyclopentadiényl)sodium se réchauffer jusqu'à la température ambiante.The (cyclopentadienyl) sodium is prepared by adding, in fractions of 5 cm 3 , a solution of cyclopentadiene (12.56 g at about 95%, 0.1805 motel in dimethoxyethane (27.1 g) at -78 ° C, to a slurry of sodium hydride (7.45 g, 0.1820 mole, dispersion in oil at 58.62%) in dimethoxyethane (98.2 g) under argon, at -2 ° C. The temperature of the reaction medium is kept between -10 and -20 ° C. by a cooling bath. The evolution of hydrogen is very important. When the addition is complete, the pink-gray (cyclopentadienyl) sodium slurry is allowed to warm up to at room temperature.

A une solution de nitrate cérique d'ammonium (0,0301 mole, 16,70 g) dans 136,9 g de diméthoxyéthane sous argon, on ajoute lentement une bouillié de (cyclopentadiényl)sodium (0,18 mole) dans 125 g de diméthoxyéthane. La réaction est effectuée à température ambiante. Il se produit une réaction légèrement exothermique qui ne nécessite pas de refroidissement. Le milieu réactionnel final est une bouillie d'un brun-doré foncé. Le mélange est maintenu sous agitation pendant toute une nuit.To a solution of ceric ammonium nitrate (0.0301 mole, 16.70 g) in 136.9 g of dimethoxyethane under argon, a slurry of (cyclopentadienyl) sodium (0.18 mole) is slowly added in 125 g of dimethoxyethane. The reaction is carried out at room temperature. A slightly exothermic reaction takes place which does not require cooling. The final reaction medium is a dark golden-brown slurry. The mixture is kept stirred overnight.

Le lendemain, on filtre le précipité, on le lave avec du diméthoxyéthane jusquà ce qu'il n'y ait plus aucun entraînement de couleur et on le sèche, ensuite, sous vide. On obtient alors 16,0 g de solide havane, presque entièrement soluble dans l'eau, présentant des traces de cérium et ayant un pH de l'ordre de 6,5, ce qui indique qu'il s'agit du nitrate de sodium attendu (15,3 g selon la théorie), tout le cérium se trouvant dans la couche organique.The following day, the precipitate is filtered, washed with dimethoxyethane until there is no longer any color entrainment and then dried, under vacuum. This gives 16.0 g of tan solid, almost entirely soluble in water, showing traces of cerium and having a pH of around 6.5, which indicates that it is sodium nitrate expected (15.3 g according to theory), all the cerium being in the organic layer.

Le filtrat est une solution brun-doré de tri(cyclopentadiényl)cérium dans le diméthoxyéthane.The filtrate is a golden-brown solution of tri (cyclopentadienyl) cerium in dimethoxyethane.

On récupère le tri(cyclopentadiényl)cérium après avoir évaporé le solvant.The tri (cyclopentadienyl) cerium is recovered after evaporating the solvent.

Exemple 2Example 2

On met en suspension 0,061 mole de (cyclopentadiényl)sodium dans 150 cm3 de diméthoxyéthane. A la température ambiante, on introduit ladite suspension en 15 minutes dans une solution de 0,03 mole de nitrate cérique d'ammonium dans 150 cm3 de diméthoxyéthane. La réaction est rapide et le solide NaN03 qui précipite, est filtré après 15 minutes.0.061 mol of (cyclopentadienyl) sodium is suspended in 150 cm 3 of dimethoxyethane. At room temperature, said suspension is introduced over 15 minutes into a solution of 0.03 mole of ceric ammonium nitrate in 150 cm 3 of dimethoxyethane. The reaction is rapid and the solid NaNO 3 which precipitates is filtered after 15 minutes.

Le filtrat contient le complexe Ce(NO3)2Cp. On évapore le diméthoxyéthane sur une fraction de la solution et l'on récupère le solide.The filtrate contains the Ce (NO 3 ) 2 Cp complex. The dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.

Sur le reste de la solution, on ajoute 2 équivalents-mole de NaAc par équivalent-mole de Ce(N03)2Cp. La réaction est rapide conduisant à 2 moles de NaN03 et 1 mole de Ce(Ac)2Cp. Après filtration, on obtient un mélange solide. On sépare Ce(Ac)zCp du NaN03 par traitement au méthanol.To the rest of the solution, 2 mole equivalents of NaAc are added per mole equivalent of Ce (N0 3 ) 2 Cp. The reaction is rapid, leading to 2 moles of NaN0 3 and 1 mole of Ce (Ac) 2 Cp. After filtration, a solid mixture is obtained. Ce (Ac) z Cp is separated from NaN0 3 by treatment with methanol.

Exemple 3Example 3

On met en suspension 0,061 mole de (cyclopentaidényl)sodium dans 150 cm3 de diméthoxyéthane. A la température ambiante, on introduit ladite suspension en 15 minutes dans une solution de 0,03 mole de nitrate cérique d'ammonium dans 150 cm3 de diméthoxyéthane. La réaction est rapide et le solide NaN03 qui précipite, est filtré après 15 minutes.0.061 mol of (cyclopentaidenyl) sodium is suspended in 150 cm 3 of dimethoxyethane. At room temperature, said suspension is introduced over 15 minutes into a solution of 0.03 mole of ceric ammonium nitrate in 150 cm3 of dimethoxyethane. The reaction is rapid and the solid NaNO 3 which precipitates is filtered after 15 minutes.

Le filtrat contient le complexe Ce(N03)2Cp. On évapore le diméthoxyéthane sur une fraction de la solution et l'on récupère le solide.The filtrate contains the Ce (N0 3 ) 2 Cp complex. The dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.

Sur le reste de la solution, on ajoute 2 équivalents-mole d'octoate de sodium par équivalent-mole de Ce(N03)2 Cp. La réaction est rapide conduisant à 2 moles de NaN03 et 1 mole de Ce(oct)2Cp. On sépare NaN03 par filtration. On isole Ce(oct)2Cp par évaparation du solvant.To the rest of the solution, 2 mole equivalents of sodium octoate are added per mole equivalent of Ce (NO 3 ) 2 Cp. The reaction is rapid, leading to 2 moles of NaN0 3 and 1 mole of Ce (oct) 2 Cp. NaN0 3 is separated by filtration. Ce (oct) 2 Cp is isolated by evaporation of the solvent.

Exemple 4Example 4

On met en suspension 0,091 mole de (cyclopentadiényl)sodium dans 150cm3 de diméthoxyéthane. A la température ambiant, on introduit ladite suspension en 15 minutes dans une solution de 0,03 mole de nitrate cérique d'ammonium dans 150 cm3 de diméthoxyéthane. La réaction est rapide et le solide NaN03 qui précipte, est filtré après 15 minutes.0.091 mol of (cyclopentadienyl) sodium is suspended in 150 cm 3 of dimethoxyethane. At ambient temperature, said suspension is introduced over 15 minutes into a solution of 0.03 mole of ceric ammonium nitrate in 150 cm 3 of dimethoxyethane. The reaction is rapid and the solid NaNO 3 which precipitates is filtered after 15 minutes.

Le filtrat contient le complexe CeNO3(Cp)2. On évapore le diméthoxyéthane sur une fraction de la solution et l'on récupère le solide.The filtrate contains the CeNO 3 (Cp) 2 complex. The dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.

Sur le reste de la solution, on ajoute 1 équivalent-mole de NaAc par équivalent-mole de CeN03(Cp)2. Après filtration, on obitent un mélange solide. On sépare CeAc(Cp)2 par traitement au méthanol.To the rest of the solution, 1 mole equivalent of NaAc is added per mole equivalent of CeN0 3 (Cp) 2 . After filtration, a solid mixture is obiter. CeAc (Cp) 2 is separated by treatment with methanol.

Exemple 5Example 5

On met en suspention 0,061 mole de (cyclopentatiényl)sodium dans 150 cm3 de diméthoxyéthane. A la température ambiante, on introduit ladite suspension en 15 minutes dans une solution de 0,03 mole de nitrate cérique d'ammonium dans 150 cm3 de diméthoxyéthane. La réaction est rapide et le solide NaN03 qui précipite, est filtré après 15 minutes.0.061 mol of (cyclopentatienyl) sodium is suspended in 150 cm 3 of dimethoxyethane. At room temperature, said suspension is introduced over 15 minutes into a solution of 0.03 mole of ceric ammonium nitrate in 150 cm 3 of dimethoxyethane. The reaction is rapid and the solid NaNO 3 which precipitates is filtered after 15 minutes.

Le filtrat contient le complexe Ce(N03)2CP. On évapore le diméthoxyéthane sur une fraction de la solution et l'on récupère le solide.The filtrate contains the Ce (N0 3 ) 2 C P complex. The dimethoxyethane is evaporated on a fraction of the solution and the solid is recovered.

Sur le reste de la solution, on ajoute 2 équivalnts-mole de

Figure imgb0001
par équivalent-mole de Ce(N03)Cp. La réaction est rapide conduisant à 2 moles de NaN03 et 1 mole de
Figure imgb0002
Après filtration, on obtient un mélange solide. On sépare
Figure imgb0003
par traitement au méthanol.To the rest of the solution, 2 mole equivalents of
Figure imgb0001
 per mole equivalent of Ce (N0 3 ) Cp. The reaction is rapid, leading to 2 moles of NaN0 3 and 1 mole of
Figure imgb0002
 After filtration, a solid mixture is obtained. We separate
Figure imgb0003
 by methanol treatment.

Exemple 6Example 6

On ajoute lentement une solution de 0,03 mole de nitrate cérique d'ammonium dans 100 g de diméthoxyéthane à une suspension de 0,1505 mole de NaCp dans du tétrahydrofuranne. Le milieu réactoinnel présente une coloration pourpre intense qui devient brun-doré foncé à la fin de l'addition du nitrate cérique d'ammonium. Après mise au reflux toute une nuit, le dégagement d'ammoniac fléchit. On filtre le NaN03 obtenu et l'on récupère Ce(Cp)3 à partir de la solution.A solution of 0.03 mole of ceric ammonium nitrate in 100 g of dimethoxyethane is slowly added to a suspension of 0.1505 mole of NaCp in tetrahydrofuran. The reaction medium has an intense purple coloration which becomes dark golden-brown at the end of the addition of ceric ammonium nitrate. After refluxing overnight, the release of ammonia declines. The NaN0 3 obtained is filtered and Ce (Cp) 3 is recovered from the solution.

Claims (17)

1. Process for the preparation of tri(cyclopentadienyl)cerium, characterized in that it consists in reacting a cyclopentadienyl complex of alkali metal with a ceric ammonium nitrate in solution in an inert organic solvent until tri(cyclopentadienyl)cerium is formed.
2. Process according to claim 1, characterized in that the solution of ceric ammonium nitrate is added to the cyclopentadienyl complex of alkali metal.
3. Process according to claim 2, characterized in that the cyclopentadienyl complex of alkali metal is in the form of a slurry in the same organic solvent.
4. Process according to claim 1, characterized in that the temperature is between approximately -10°C and approximately 250°C.
5. Process according to claim 1, characterized in that the reaction is carried out at the reflux temperature of the inert organic solvent.
6. Process according to claim 1, characterized in that the cyclopentadienyl complex of alkali metal is (cyclopentadienyl)sodium.
7. Process according to claim 1, characterized in that the alkali metal nitrate formed during the reaction is separated off by filtration and that the (cyclopentadienyl)cerium is recovered from the filtrate.
8. Process for the preparation of tri(cyclopentadienyl)cerium and of the mono- and di(cyclopentadienyl)cerium intermediates, characterized in that it consists in adding a cyclopentadienyl complex of alkali metal to a solution of ceric ammonium nitrate, forming successively and in stages, mono(cyclopentadienyl)cerium dinitrate, di(cyclopentadienyl)cerium mononitrate and tri(cyclopentadienyl)cerium.
9. Process according to claim 8, characterized in that it is carried out in the presence of a sufficient quantity of cyclopentadienyl complex of alkali metal to form mono(cyclopentadienyl)cerium dinitrate.
10. Process according to claim 8, characterized in that it is carried out in the presence of a sufficient quantity of cyclopentadienyl complex of alkali metal to form di(cyclopentadienyl)cerium mononitrate.
11. Process according to claim 8, characterized in that it is carried out in the presence of a sufficient quantity of cyclopentadienyl complex of alkali metal to form tri(cyclopentadienyl)cerium.
12. Process according to claim 8, characterized in that the cyclopentadienyl complex of alkali metal is added to the solution of ceric ammonium nitrate.
13. Process according to claim 8, characterized in that the cyclopentadienyl complex of alkali metal is in the form of a slurry in the same organic solvent.
14. Process according to claim 8, characterized in that the temperature is between approximately -10°C and approximately 250°C.
15. Process according to claim 8, characterized in that it is carried out in the presence of a sufficient quantity of inert organic solvent to dissolve the ceric ammonium nitrate and the (cyclopentadienyl)cerium formed.
16. Mono(cyclopentadienyl)cerium dinitrate.
17. Di(cyclopentadienyl)cerium mononitrate.
EP85400829A 1984-04-27 1985-04-26 Tri(cyclopentadienyl)cerium and process for its preparation Expired EP0165100B1 (en)

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